The invention relates to new conjugated mono-, oligo- and polyalkylidenefluorenes. The invention further relates to methods for their preparation, their use as semiconductors or charge transport materials in optical, electrooptical or electronic devices including field effect transistors, electroluminescent, photovoltaic and sensor devices. The invention further relates to field effect transistors and semiconducting components comprising the new mono-, oligo- and polymers.
Organic materials have recently shown promise as the active layer in organic based thin film transistors and organic field effect transistors [see H. E. Katz, Z. Bao and S. L. Gilat, Acc. Chem. Res., 2001, 34, 5, 359]. Such devices have potential applications in smart cards, security tags and the switching element in flat panel displays. Organic materials are envisaged to have substantial cost advantages over their silicon analogues if they can be deposited from solution, as this enables a fast, large-area fabrication route.
The performance of the device is principally based upon the charge carrier mobility of the semiconducting material and the current on/off ratio, so the ideal semiconductor should have a low conductivity in the off state, combined with a high charge carrier mobility ( greater than 1xc3x9710xe2x88x923 cm2Vxe2x88x921 sxe2x88x921). In addition, it is important that the semiconducting material is relatively stable to oxidation, i.e., it has a high ionisation potential, as oxidation leads to reduced device performance.
A known compound which has been shown to be an effective p-type semiconductor for OFETs is pentacene [see S. F. Nelson, Y. Y. Lin, D. J. Gundlach and T. N. Jackson, Appl. Phys. Lett., 1998, 72, 1854].
When deposited as a thin film by vacuum deposition, it was shown to have carrier mobilities in excess of 1 cm2 Vxe2x88x921 sxe2x88x921 with very high current on/off ratios greater than 106. However, vacuum deposition is an expensive processing technique that is unsuitable for the fabrication of large-area films.
Regular poly(3-hexylthiophene) has been reported with charge carrier mobility between 1xc3x9710xe2x88x925 and 4.5xc3x9710xe2x88x922 cm2 Vxe2x88x921 sxe2x88x921, but with a rather low current on/off ratio between 10 and 103 [see Z. Bao et al., Appl. Pys. Lett. 1997, 78, 2184]. In general, poly(3-alkylthiophenes) show improved solubility and are able to be solution processed to fabricate large area films. However, poly(3-alkylthiophenes) have relatively low ionisation potentials and are susceptible to doping in air [see H. Sirringhaus et al., Adv. Solid State Phys. 1999, 39, 101].
It is an aim of the present invention to provide new materials for use as semiconductors or charge transport materials, which are easy to synthesize, have high charge mobility, good processibility and improved oxidative stability. Other aims of the invention are immediately evident to those skilled in the art from the following description.
The inventors have found that these aims can be achieved by providing new monomers, oligomers and polymers based on 9-alkylidenefluorene (1). Poly(9-alkylidenefluorenes) (2) exhibit a high degree of planarity in the backbone due to the carbon sp2 hybridisation at the 9 position, in comparison with for example poly(9,9-dialkylfluorenes), and strong interchain pi-pi-stacking interactions making them effective charge transport materials with high carrier mobilities. In addition, the high resonance stability of the fused phenylene structure leads to a high ionisation potential and hence good stability. Also, the incorporation of alkyl substitutents R1, R2 into the alkylidenefluorene group leads to good solubility and thus good solution processibility of the materials according to the present invention. Solution processing during device manufacture has the advantage over vaccum deposition of being a potentially cheaper and faster technique. 
The synthesis of polyfluorenes and poly(9,9-dialkylfluorenes) for use in light emitting diodes have been reported in prior art, for example in U.S. Pat. No. 6,169,163. Furthermore, U.S. Pat. No. 6,169,163 discloses monosubstituted 9-alkylidenefluorenes (1) and poly(9-alkylidenefluorenes) (2) (R1=alkyl, R2=H). Copolymers of disubstituted 9-alkylidenefluorenes (R1=R2=alkyl optionally substituted) are disclosed in WO 00/46321, although no examples or method for the preparation of monomer 1 is disclosed. The synthesis of specific monosubstituted 9-alkylidenefluorenes (1) (R1=alkyl, R2=H) is also described in K. Subba Reddy et al., Synthesis, 2000, 1, 165. The synthesis of specific disubstituted 9-alkylidenefluorenes (1) (R1=methyl, R2=methyl or phenyl) is disclosed in K. C. Gupta et al., Indian J. Chem., Sect. B, 1986, 25B, 1067. The synthesis of a specific copolymer of disusbtituted 9-alkylidenefluorene (1) (R1=methyl, R2=ethyl) is reported by M. Ranger and M. Leclerc, Macromolecules 1999, 32, 3306. These two methods are not readily amenable to the preparation of molecules with alkyl chains larger than propyl. Moreover, polymers of unsymmetrical 9-alkylidenefluorenes have the general problem of poor regioregularity and therefore poor ordering and packing in the solid state. Mono- and poly(9-alkylidenefluorenes) according to the present invention have not been reported.
A further aspect of the invention relates to reactive mesogens having a central core comprising one or more 9-alkylidene-fluorene units, and optionally contain further unsaturated organic groups that form a conjugated system together with the 9-alkylidenefluorene units, said core being linked, optionally via a spacer group, to one or two polymerisable groups. The reactive mesogens can induce or enhance liquid crystal phases or are liquid crystalline themselves. They can be oriented in their mesophase and the polymerisable group(s) can be polymerised or crosslinked in situ to form polymer films with a high degree of order, thus yielding improved semiconductor materials with high stability and high charge carrier mobility.
Grell et al., J. Korean Phys. Soc. 2000, 36(6), 331 suggest a reactive mesogen comprising a conjugated distyrylbenzene core with two reactive acrylate end groups as a model compound for molecular electronics. However, there is no disclosure of reactive mesogens of 9-alkylidenefluorene.
A further aspect of the invention relates to liquid crystal polymers, in particular liquid crystal side chain polymers obtained from the reactive mesogens according to the present invention, which are then further processed, e.g., from solution as thin layers for use in semiconductor devices.
Definition of Terms
The terms xe2x80x98liquid crystalline or mesogenic materialxe2x80x99 or xe2x80x98liquid crystalline or mesogenic compoundxe2x80x99 means materials or compounds comprising one or more rod-shaped, lath-shaped or disk-shaped mesogenic groups, i.e., groups with the ability to induce liquid crystal phase behaviour. The compounds or materials comprising mesogenic groups do not necessarily have to exhibit a liquid crystal phase themselves. It is also possible that they show liquid crystal phase behaviour only in mixtures with other compounds, or when the mesogenic compounds or materials, or the mixtures thereof, are polymerised.
The term xe2x80x98polymerisablexe2x80x99 includes compounds or groups that are capable of participating in a polymerisation reaction, like radicalic or ionic chain polymerisation, polyaddition or polycondensation, and reactive compounds or reactive groups that are capable of being grafted for example by condensation or addition to a polymer backbone in a polymeranaloguous reaction.
The term xe2x80x98filmxe2x80x99 includes self-supporting, i.e., free-standing, films that show more or less pronounced mechanical stability and flexibility, as well as coatings or layers on a supporting substrate or between two substrates.
The invention relates to mono-, oligo- and polymers of formula I
R9xe2x80x94[(A)axe2x80x94(B)bxe2x80x94(C)c]nxe2x80x94R10xe2x80x83xe2x80x83I
wherein
A and C are independently of each other xe2x80x94CX1xe2x95x90CX2xe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, or optionally substituted arylene or heteroarylene,
X1 and X2 are independently of each other H, F, Cl or CN,
B is a group of formula II 
R1 and R2 are independently of each other halogen, straight chain, branched or cyclic alkyl with 1 to 20 C-atoms, which may be unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, it being also possible for one or more non-adjacent CH2 groups to be replaced, in each case independently from one another, by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94NR0xe2x80x94, xe2x80x94SiR0R00xe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94, xe2x80x94OCOxe2x80x94Oxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94Sxe2x80x94COxe2x80x94, xe2x80x94COxe2x80x94Sxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94 or xe2x80x94Cxe2x89xa1Cxe2x80x94 in such a manner that O and/or S atoms are not linked directly to one another, optionally substituted aryl or heteroaryl, or Pxe2x80x94Spxe2x80x94X,
R3 to R10 are independently of each other H or have one of the meanings given for R1,
R0 and R00 are independently of each other H or alkyl with 1 to 12 C-atoms,
P is a polymerisable or reactive group,
Sp is a spacer group or a single bond, and
X is xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94OCH2xe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94, xe2x80x94OCOxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94NR0xe2x80x94, xe2x80x94NR0xe2x80x94COxe2x80x94, xe2x80x94OCH2xe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94SCH2xe2x80x94, xe2x80x94CH2Sxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94COOxe2x80x94, xe2x80x94OOCxe2x80x94CHxe2x95x90CHxe2x80x94 or a single bond,
a, b and c are independently of each other 0 or 1, with a+b+c greater than 0, and wherein in at least one recurring unit [(A)axe2x80x94(B)bxe2x80x94(C)c] b is 1, and
n is an integer xe2x89xa71,
wherein the recurring units [(A)axe2x80x94(B)bxe2x80x94(C)c] can be identical or different, and
with the provisos that
a) in case n is 1, a and c are 0, R3-8 are H, and one of R1 and R2 is methyl and the other is methyl, ethyl or phenyl, R9 and R10 are not at the same time Cl or Br, and
b) A and C are different from 2,7-(4-hexylphenyl)fluorene-9-carbonyl.
The invention further relates to a process of preparing monomers of formula I wherein n is 1, very preferably monomers of formula II-1 
wherein R1 to R10 are as defined above, in particular wherein R9 and R10 are independently of each other halogen.
The invention further relates to the use of mono-, oligo- and polymers according to the invention as semiconductors or charge transport materials, in particular in optical, electrooptical or electronic devices, like for example components of integrated circuitry, field effect transistors (FET) for example as thin film transistors in flat panel display applications or for Radio Frequency Identification (RFID) tags, or in semiconducting components for organic light emitting diode (OLED) applications such as electroluminescent displays or backlights of, e.g., liquid crystal displays, for photovoltaic or sensor devices, as electrode materials in batteries, as photoconductors and for electrophotographic applications like electrophotographic recording.
The invention further relates to a field effect transistor, for example as a component of integrated circuitry, as a thin film transistor in flat panel display applications, or in a Radio Frequency Identification (RFID) tag, comprising one or more mono-, oligo- or polymers according to the invention.
The invention further relates to a semiconducting component, for example in OLED applications like electroluminescent displays or backlights of, e.g., liquid crystal displays, in photovoltaic or sensor devices, as electrode materials in batteries, as photoconductors and for electrophotographic applications, comprising one or more mono-, oligo- or polymers according to the invention.
The invention further relates to a security marking or device comprising an RFID or ID tag or a FET according to the invention.